[go: up one dir, main page]

CN105745018A - 用于制备加氢处理催化剂的方法 - Google Patents

用于制备加氢处理催化剂的方法 Download PDF

Info

Publication number
CN105745018A
CN105745018A CN201480061232.6A CN201480061232A CN105745018A CN 105745018 A CN105745018 A CN 105745018A CN 201480061232 A CN201480061232 A CN 201480061232A CN 105745018 A CN105745018 A CN 105745018A
Authority
CN
China
Prior art keywords
carrier
weight
phosphorus
molybdenum
cobalt
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201480061232.6A
Other languages
English (en)
Other versions
CN105745018B (zh
Inventor
F·文特
J·A·范威尔塞内斯
M·S·里古托
P·J·A·M·吉尔泰
J·J·M·范维兰德伦
A·阿兹格海
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shell Internationale Research Maatschappij BV
Original Assignee
Shell Internationale Research Maatschappij BV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shell Internationale Research Maatschappij BV filed Critical Shell Internationale Research Maatschappij BV
Publication of CN105745018A publication Critical patent/CN105745018A/zh
Application granted granted Critical
Publication of CN105745018B publication Critical patent/CN105745018B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • B01J21/04—Alumina
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B01J35/32—Bulk density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0203—Impregnation the impregnation liquid containing organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0236—Drying, e.g. preparing a suspension, adding a soluble salt and drying
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/024—Multiple impregnation or coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/082—Decomposition and pyrolysis
    • B01J37/088—Decomposition of a metal salt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/20—Sulfiding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
    • B01J2523/31—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/50—Constitutive chemical elements of heterogeneous catalysts of Group V (VA or VB) of the Periodic Table
    • B01J2523/51—Phosphorus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/60—Constitutive chemical elements of heterogeneous catalysts of Group VI (VIA or VIB) of the Periodic Table
    • B01J2523/68—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0202—Alcohols or phenols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/31—Density
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

用于制备加氢处理催化剂的方法，所述加氢处理催化剂含有5wt％?50wt％的钼、0.5wt％?20wt％的钴和0?5wt％的磷，全部基于催化剂的总干重，所述方法包括(a)用钼、钴和基于载体重量1?60wt％的葡萄糖酸，以及任选的磷来处理含镍载体，(b)任选地，在40?200℃温度下干燥处理的载体，以及(c)在200?650℃的温度下煅烧所述处理的且任选干燥的载体，以获得煅烧的处理的载体。

Description

用于制备加氢处理催化剂的方法
发明领域
本发明涉及一种用于制备加氢处理催化剂的方法。
发明背景
在烃原料(如原油、馏出油和残留原油馏分)的催化加氢处理中，含有氢化金属的催化剂组合物用于促进脱硫和脱氮反应，并由此提供从烃原料中除去有机硫和有机氮化合物。所述方法涉及在高温和高压下且在氢气存在下，使催化剂颗粒与烃原料接触，以将原料的硫组分转化为硫化氢并且将原料的氮组分转化为氨。随后除去硫化氢和氨，生成加氢处理产物。
加氢处理催化剂包含高熔点氧化物上的氢化金属组分。氢化金属组分通常为第VI族金属组分，例如钼和/或钨，以及第VIII族金属组分，例如镍和/或钴。多孔高熔点氧化物负载材料通常可以是氧化铝。促进剂如磷也可用作加氢处理催化剂的组分。
对进一步改进这些催化剂的性能具有持续兴趣。
可导致改进性能的方法是用含有催化活性金属和有机配体的溶液处理载体，并随后干燥所处理的载体。通过不煅烧这种干燥的催化剂，可获得如出版物例如EP-A-0482818、WO-A-96/41848、WO2009/020913和WO2012/021389中所述的改进性能。制备仅干燥但不煅烧的催化剂在实际商业实践中是相对复杂且繁琐的。
本发明的目的是寻找一种在低硫低氮燃料如超低硫柴油的生产中相对易于使用同时提供具有良好活性的加氢处理催化剂的方法。
发明概述
已经发现，可通过用进一步包含葡萄糖酸的含金属的浸渍溶液处理载体实现此目的。
因此，本发明涉及一种用于制备加氢处理催化剂的方法，所述加氢处理催化剂包含5wt％-50wt％的钼、0.5wt％-20wt％的钴和0-5wt％的磷，全部基于催化剂的总干重，所述方法包括：
(a)用钼、钴，和基于载体重量1-60wt％的葡萄糖酸，以及任选的磷来处理含镍载体，
(b)任选地，在40-200℃的温度下干燥处理的载体，以及
(c)在200-650℃的温度下煅烧所处理的且任选干燥的载体，以获得煅烧处理的载体。
根据本方法，可借助于涉及有限数量的方法步骤的相对简单的方法来制备加氢处理催化剂。除易于生产之外，本发明具有下列优势：发现获得的催化剂在加氢脱硫中具有高活性。
发明详述
含镍载体的适合实例包括二氧化硅、氧化铝、二氧化钛、氧化锆、二氧化硅-氧化铝、二氧化硅-二氧化钛、二氧化硅-氧化锆、二氧化钛-氧化铝、氧化锆-氧化铝、二氧化硅-二氧化钛及其两种或更多种的组合，条件是这些包含镍。载体优选为含镍氧化铝，更优选为包含0.1-5wt％镍、更特别0.2-3wt％镍的氧化铝，其作为金属基于干燥载体的总量进行计算。
多孔催化剂载体可具有5-35nm范围内的平均孔径，其根据测试ASTMD-4222测量。多孔高熔点氧化物的总孔体积优选在0.2-2ml/g范围内。
多孔高熔点氧化物的表面积，如通过B.E.T.法测量，通常超过100m2/g，并且其一般在100-400m2/g范围内。根据ASTM测试D3663-03，通过B.E.T.法来测量表面积。
催化剂包含载体上的催化活性金属。这些催化活性金属是钼与钴的组合。优选还存在磷。因此，处理的氧化铝载体优选由钼、磷、葡萄糖酸和钴组成。
金属组分可以是金属本身或含有金属的任意组分，包括但不限于金属氧化物、金属氢氧化物、金属碳酸盐和金属盐。
对于钴，金属组分优选选自醋酸盐、甲酸盐、柠檬酸盐、氧化物、氢氧化物、碳酸盐、硝酸盐、硫酸盐，及其两种或更多种。优选地，钴组分是金属硝酸盐。
对于钼，优选的金属盐是钼氧化物和钼硫化物，更优选是还含有铵的盐，例如七钼酸铵和二钼酸铵。
使用的磷化合物优选选自磷的酸(例如偏磷酸、焦磷酸、正磷酸和亚磷酸)以及磷的酸的前体。该前体是能够在水的存在下形成至少一个酸性氢原子的含磷化合物。优选的前体是磷氧化物和磷。优选的磷的酸是正磷酸(H3PO4)。
基于加氢处理催化剂的总干重并基于金属，钴可以以0.5wt％-20wt％、优选1wt％-15wt％、并且最优选2wt％-12wt％范围内的量存在于加氢处理催化剂中。
基于催化剂的总干重并基于金属，钼可以以5wt％-50wt％、优选8wt％-40wt％、并且最优选10wt％-30wt％范围内的量存在于加氢处理催化剂中。
基于催化剂的总干重并基于磷，磷可以以0.1wt％-5wt％、优选0.2wt％-5wt％、并且更优选0.5wt％-4.5wt％范围内的量存在于加氢处理催化剂中，。最优选地，磷的量为1.5-3.5wt％，其基于催化剂的总干重。
金属通常以氧化物或硫化物的形式存在。为了确定金属含量，不管其实际形式或状态如何，假设它们以金属本身的形式存在。干重是假设所有挥发性化合物如水和葡萄糖酸已经被除去的重量。可以通过使催化剂保持在400℃温度下至少2小时来确定干重。为了计算磷含量，不管其实际形式如何，假设磷作为元素存在。
葡萄糖酸的量基于干载体的重量优选是2-40wt％葡萄糖酸，更优选3-30wt％，更特别为4-20wt％。
优选的加氢处理催化剂由在载体上的0.5wt％-20wt％的钴、5wt％-50wt％的钼和0.1-5wt％的磷组成，所述载体由氧化铝和0.1-5wt％的镍组成。
催化活性金属、葡萄糖酸和磷优选通过用含有这些组分的溶液处理载体来引入到载体中。最优选地，使用含有这些组分的溶液通过孔体积浸渍添加所述组分。优选所有组分存在于单一溶液中，最优选水溶液。可能并不是所有组分混合在单一浸渍溶液中，例如由于稳定性问题。在此情况下，可优选使用两种或更多种溶液，任选地中间有干燥步骤。
本发明涉及用葡萄糖酸处理载体。这可以是葡萄糖酸或葡萄糖酸的盐或葡萄糖酸的酯，所述酯在溶液中形成葡萄糖酸(盐)(gluconate)。如果溶液用于处理载体，所述溶液通常除了葡萄糖酸本身以外还可能包含葡萄糖酸的盐。对于本发明，用葡萄糖酸的盐处理载体也被认为是用葡萄糖酸处理载体。优选地，通过向溶剂添加葡萄糖酸来制备用于处理载体的溶液。
优选地，葡萄糖酸的重量与沉积于载体上的钴和钼的总重量的比率是0.1-5，更特别0.1-3，更特别0.2-3，更优选0.3-2.5，更优选0.5-2，更优选0.6-1.8，最优选0.7-1.5。
在步骤(b)中，可在步骤(c)的煅烧之前干燥处理的载体。干燥是否确实应该进行，并且如果应该，在什么样的条件下，这取决于存在的挥发性组分的量和随后的煅烧条件。通常，干燥将在40-200℃的温度下进行0.1-6小时，更特别在100-200℃的温度下进行0.5-4小时。
步骤(c)的煅烧优选在200-650℃的温度下进行0.1-6小时的期间，更特别在250-600℃、更特别280-550℃的温度下进行0.5-4小时的期间。
不希望受任何理论约束，据信改善的性能是由于催化活性金属、载体和葡萄糖酸之间的相互作用。据信在煅烧作用下，相互作用导致更小的金属氧化物颗粒，在硫化期间维持所述更小的颗粒尺寸。
在用于加氢处理之前，煅烧处理的载体优选被硫化。因此，本发明的方法优选进一步包括：(d)硫化煅烧处理的载体以获得加氢处理催化剂。
硫化之后(所述硫化可原位或非原位进行)，其被认为是易于用于商业用途的催化剂。
本发明还提供了一种用于加氢处理含硫烃原料的方法，所述方法包括，使烃原料在1-70巴的氢分压和200-420℃的温度下，与根据本发明获得的催化剂接触。
可利用本领域技术人员已知的任何常规方法来进行煅烧处理的载体的硫化。因此，煅烧处理的载体可与包含硫化氢和氢气的气态流接触。在另一个实施方式中，煅烧处理的载体与含硫化合物接触，所述含硫化合物在本发明的接触条件下可分解成硫化氢。此类可分解化合物的实例包括硫醇类、CS2、噻吩类、二甲基硫醚(DMS)和二甲基二硫醚(DMDS)。进一步和优选的选项是通过使组合物在适合的硫化处理条件下与包含含硫化合物的烃原料接触来完成硫化。烃原料的含硫化合物可以是有机硫化合物，特别是通常包含于通过加氢脱硫法生产的石油馏出物中的那种。通常，硫化温度在150-450℃、优选175-425℃、以及最优选200-400℃的范围内。
硫化压力可以在1巴-70巴、优选1.5巴-55巴，以及最优选2巴-45巴的范围内。
本发明更详细地解释于以下实施例中。
实施例
实施例1-含钴/钼催化剂
通过将拟薄水铝石挤成1.3mm三叶型并干燥和煅烧这些以提供如表1所述的氧化铝载体，来制备商业载体。对于载体1的制备，在挤出之前将拟薄水铝石与1wt％的镍粉混合。
根据ASTM测试D-4222测量平均孔径。根据ASTM测试D-366303测量表面积。镍含量是基于干燥载体总重量的金属重量。
表1-氧化铝载体性质
通过孔体积浸渍将催化剂的金属组分引入载体，以产生以下金属组合物(金属重量基于催化剂的总干重)：14％Mo、3.5％Co、2.25％P。浸渍溶液包括磷酸、碳酸钴、三氧化钼和葡萄糖酸。所得溶液的总体积等于氧化铝载体的水孔体积的98％。浸渍溶液中的葡萄糖酸浓度是10-25wt％，相当于基于载体的葡萄糖酸含量为9-12.5wt％。
然后在110℃干燥浸渍的载体2小时，并随后在高于300℃的温度下煅烧2小时，以除去葡萄糖酸。
获得以下催化剂。
表2-Co/Mo催化剂
实施例2-催化剂活性
滴流式微反应器用于测试根据本发明的催化剂相对于商业参考催化剂(包含相当量的钴和钼并具有0.72ml/g压实体积密度的对比催化剂I)的脱硫活性。
组合物通过使它们与含有硫增敏剂(spikingagent)的液态烃接触而进行调整和硫化，以提供2.5wt％的硫含量。这些测试中所用的方法条件包括300NI/kg的气-油比、40巴的压力以及1h-1的液时空速。将加权平均床温度(WABT)调节至340-380℃范围内的温度。
用于测试的进料为含有1.28wt％硫的全馏程气油。
方法条件和进料性质代表了典型的超低硫柴油(ULSD)操作。
假定反应级数为1.25，确定了每种组合物的速率常数。确定了根据本发明的每种组合物相对于对比催化剂I的相对体积活性(RVA)。表3给出了获得含10ppm硫的产品所需的温度。实现此硫含量和较高RVA所需的较低温度表明根据本发明的催化剂相对于对比商业催化剂I具有改善的性能。
表3-加氢脱硫活性

Claims (8)

1.用于制备加氢处理催化剂的方法，所述加氢处理催化剂包含5wt％-50wt％的钼、0.5wt％-20wt％的钴和0-5wt％的磷，全部基于催化剂的总干重，所述方法包括
(a)用钼、钴和基于载体重量1-60wt％的葡萄糖酸，和任选的磷来处理含镍载体，
(b)任选地，在40-200℃的温度下干燥所述处理的载体，和
(c)在200-650℃的温度下煅烧所述处理的且任选干燥的载体，以获得煅烧的处理的载体。
2.根据权利要求1所述的方法，在所述方法中，所述葡萄糖酸的量基于载体的总干重为2-40wt％。
3.根据权利要求1或2所述的方法，其中，所述磷的量基于催化剂的总干重为1.5-3.5wt％。
4.根据权利要求1-3任一项所述的方法，其中所述载体是氧化铝。
5.根据前述权利要求任一项所述的方法，其中所述加氢处理催化剂由载体上的1wt％-15wt％的钴、8wt％-40wt％的钼和0.1-5wt％的磷组成，所述载体由氧化铝和0.1-5wt％的镍组成，所有金属基于催化剂的总干重。
6.根据前述权利要求任一项所述的方法，其中，葡萄糖酸的重量与沉积在所述载体上的钴和钼的总重量的比率在煅烧之前是0.1-5。
7.根据前述权利要求任一项所述的方法，所述方法进一步包括
(d)硫化所述煅烧的处理的载体，以获得所述加氢处理催化剂。
8.用于加氢处理含硫烃原料的方法，所述方法包括使所述烃原料在1-70巴的氢分压和200-420℃的温度下，与根据权利要求7获得的催化剂接触。
CN201480061232.6A 2013-11-07 2014-11-04 用于制备加氢处理催化剂的方法 Active CN105745018B (zh)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP13191902 2013-11-07
EP13191902.9 2013-11-07
PCT/EP2014/073637 WO2015067583A1 (en) 2013-11-07 2014-11-04 Process for preparing a hydrotreating catalyst

Publications (2)

Publication Number Publication Date
CN105745018A true CN105745018A (zh) 2016-07-06
CN105745018B CN105745018B (zh) 2019-04-19

Family

ID=49518861

Family Applications (3)

Application Number Title Priority Date Filing Date
CN201480061232.6A Active CN105745018B (zh) 2013-11-07 2014-11-04 用于制备加氢处理催化剂的方法
CN201480061233.0A Pending CN105745019A (zh) 2013-11-07 2014-11-04 制备加氢处理催化剂的方法
CN202010512267.4A Pending CN111632613A (zh) 2013-11-07 2014-11-04 制备加氢处理催化剂的方法

Family Applications After (2)

Application Number Title Priority Date Filing Date
CN201480061233.0A Pending CN105745019A (zh) 2013-11-07 2014-11-04 制备加氢处理催化剂的方法
CN202010512267.4A Pending CN111632613A (zh) 2013-11-07 2014-11-04 制备加氢处理催化剂的方法

Country Status (9)

Country Link
US (2) US10118160B2 (zh)
EP (2) EP3065867B1 (zh)
KR (2) KR102277834B1 (zh)
CN (3) CN105745018B (zh)
BR (2) BR112016010262B1 (zh)
CA (2) CA2927118C (zh)
RU (2) RU2678578C2 (zh)
SG (2) SG11201603197TA (zh)
WO (2) WO2015067583A1 (zh)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113559870A (zh) * 2020-04-28 2021-10-29 中国石油化工股份有限公司 重油加氢催化剂及其制备方法和应用

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2626402C1 (ru) * 2016-11-09 2017-07-27 Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук (ИК СО РАН) Способ приготовления катализатора гидроочистки сырья гидрокрекинга
RU2644563C1 (ru) * 2017-09-25 2018-02-13 Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук (ИК СО РАН) Катализатор гидроочистки сырья гидрокрекинга
RU2649384C1 (ru) * 2017-09-25 2018-04-05 Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук (ИК СО РАН) Способ гидроочистки сырья гидрокрекинга
WO2021038436A1 (en) * 2019-08-26 2021-03-04 Reliance Industries Limited A catalyst system and method for its preparation
CN112718011B (zh) * 2019-10-28 2022-06-07 中国石油化工股份有限公司 一种加氢处理催化剂及其制备方法
WO2022201179A1 (en) 2021-03-20 2022-09-29 Hindustan Petroleum Corporation Limited A dispersed hydrotreating catalyst and a process of preparation thereof
WO2023170700A1 (en) * 2022-03-11 2023-09-14 Hindustan Petroleum Corporation Limited Naphtha hydrotreating catalyst and process of preparation thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050261124A1 (en) * 2004-05-19 2005-11-24 National Institute Of Advanced Industrial Science And Technology Hydrotreating catalyst of catalytic cracking gasoline
CN101330972A (zh) * 2005-12-14 2008-12-24 先进炼制技术有限公司 制备加氢处理催化剂的方法
WO2013092806A1 (en) * 2011-12-23 2013-06-27 Shell Internationale Research Maatschappij B.V. Process for preparing hydrocracking catalyst
CN103182310A (zh) * 2011-12-28 2013-07-03 中国石油天然气股份有限公司 一种馏分油加氢处理催化剂制备方法

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3244693B2 (ja) 1990-10-17 2002-01-07 住友金属鉱山株式会社 炭化水素油の水素化処理用触媒の製造方法
JP3802106B2 (ja) 1995-06-08 2006-07-26 日本ケッチェン株式会社 炭化水素油の水素化処理触媒とその製造方法およびその活性化方法
US7208446B2 (en) * 1999-08-11 2007-04-24 Albemarle Netherlands B. V. Quasi-crystalline boehmites containing additives
AU2003254948A1 (en) * 2002-08-20 2004-03-11 National Institute Of Advanced Industrial Science And Technology Catalyst for hydrodesulfurization of hydrocarbon
HUE059665T2 (hu) * 2003-10-03 2022-12-28 Albemarle Netherlands Bv Eljárás hidrogénezõ katalizátor aktiválására
JP2005262063A (ja) * 2004-03-17 2005-09-29 National Institute Of Advanced Industrial & Technology 水素化処理触媒
US7820036B2 (en) * 2006-08-03 2010-10-26 Shell Oil Company Highly stable heavy hydrocarbon hydrodesulfurization catalyst and methods of making and use thereof
JP2010535620A (ja) 2007-08-06 2010-11-25 シエル・インターナシヨナル・リサーチ・マートスハツペイ・ベー・ヴエー 炭化水素原料の接触水素化処理において有用な組成物、このような触媒の製造方法、およびこのような触媒の使用方法
CN101376110B (zh) * 2007-08-27 2010-08-18 中国石油化工股份有限公司 一种加氢催化剂的制备方法
JP5150540B2 (ja) * 2009-03-23 2013-02-20 Ｊｘ日鉱日石エネルギー株式会社 炭化水素油の水素化精製方法
CN102361692B (zh) * 2009-03-23 2013-12-18 吉坤日矿日石能源株式会社 加氢精制用催化剂及其制造方法、烃油的加氢精制方法
IN2012DN01391A (zh) * 2009-08-24 2015-06-05 Albemarle Europe Sprl
US9376637B2 (en) 2010-08-13 2016-06-28 Shell Oil Company Method of making a hydroprocessing catalyst with a single step metal and chelant incorporation, the catalyst, and the use of the catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20050261124A1 (en) * 2004-05-19 2005-11-24 National Institute Of Advanced Industrial Science And Technology Hydrotreating catalyst of catalytic cracking gasoline
CN101330972A (zh) * 2005-12-14 2008-12-24 先进炼制技术有限公司 制备加氢处理催化剂的方法
WO2013092806A1 (en) * 2011-12-23 2013-06-27 Shell Internationale Research Maatschappij B.V. Process for preparing hydrocracking catalyst
CN103182310A (zh) * 2011-12-28 2013-07-03 中国石油天然气股份有限公司 一种馏分油加氢处理催化剂制备方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113559870A (zh) * 2020-04-28 2021-10-29 中国石油化工股份有限公司 重油加氢催化剂及其制备方法和应用

Also Published As

Publication number Publication date
EP3065867C0 (en) 2023-09-20
KR20160085248A (ko) 2016-07-15
RU2016120009A (ru) 2017-12-12
CA2926759C (en) 2021-11-30
EP3065868B1 (en) 2023-06-07
RU2016119985A (ru) 2017-12-12
KR102277831B1 (ko) 2021-07-15
US9993809B2 (en) 2018-06-12
RU2678456C2 (ru) 2019-01-29
US10118160B2 (en) 2018-11-06
CA2927118C (en) 2021-12-07
BR112016010262B1 (pt) 2024-01-23
WO2015067583A1 (en) 2015-05-14
SG11201603195XA (en) 2016-05-30
RU2016120009A3 (zh) 2018-06-06
BR112016010262A8 (pt) 2020-09-24
EP3065868A1 (en) 2016-09-14
BR112016008615A2 (zh) 2017-08-01
CA2926759A1 (en) 2015-05-14
KR20160083864A (ko) 2016-07-12
EP3065867B1 (en) 2023-09-20
EP3065867A1 (en) 2016-09-14
RU2016119985A3 (zh) 2018-06-07
EP3065868C0 (en) 2023-06-07
CN111632613A (zh) 2020-09-08
CN105745018B (zh) 2019-04-19
CN105745019A (zh) 2016-07-06
KR102277834B1 (ko) 2021-07-15
BR112016008615B1 (pt) 2021-09-08
RU2678578C2 (ru) 2019-01-30
WO2015067585A1 (en) 2015-05-14
US20160264879A1 (en) 2016-09-15
CA2927118A1 (en) 2015-05-14
US20160271594A1 (en) 2016-09-22
SG11201603197TA (en) 2016-05-30

Similar Documents

Publication Publication Date Title
US10118160B2 (en) Process for preparing a hydrotreating catalyst
TWI629100B (zh) 包含雜環極性化合物之氫化處理觸媒組合物、製造該觸媒之方法及使用該觸媒之方法
JP2010535620A (ja) 炭化水素原料の接触水素化処理において有用な組成物、このような触媒の製造方法、およびこのような触媒の使用方法
TW201427769A (zh) 包含釩之渣油加氫處理催化劑及其於渣油加氫轉化製程中之用途
CN105478129A (zh) 一种加氢处理催化剂及其应用
KR20140050013A (ko) 탄화수소의 촉매 수소화공정에 유용한, 활성 금속 또는 전구체, 아민 성분 및 아민 비-함유 극성 첨가제를 갖는 조성물, 그 조성물의 제조 방법
KR102012055B1 (ko) 탄화수소의 촉매 수소화공정에 유용한 에테르 아민 첨가제 함침된 조성물, 그 조성물의 제조 방법
US11517891B2 (en) Hydroprocessing catalyst having an organic additive with metals incorporated using chelant and method of making and using such catalyst
US8921254B2 (en) Hydroprocessing catalyst and methods of making and using such a catalyst
CN107073459A (zh) 含有乙酰乙酸化合物的加氢处理催化剂组合物、制备这种催化剂的方法和使用这种催化剂的方法

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant